THE CATALYTIC PREPARATION OF HYDROXYLAMINE
VALENTINE AUSTIN JONES
B. S. University of Illinois
Submitted in Partial Fulfillment of the
Requirements for the Degree of
MASTER OF SCIENCE
THE GRADUATE SCHOOL
UNIVERSITY OF ILLINOIS
UNIVERSITY OF ILLINOIS
THE GRADUATE SCHOOL
Ja nuary 19, 192J?
I HEREBY RECOMMEND THAT THE THESIS PREPARED UNDER MY
Valenti n s Aust in jLcnes
ENTITLED The Catalytic Preparation cf K ydroxylarjjn e
BE ACCEPTED AS FULFILLING THIS PART OF THE REQUIREMENTS FOR
THE DEGREE OF jjas t ery_of Science
Recommendation concurred in*
*Required for doctor’s degree but not for master’s
Digitized by the Internet Archive
The writer wishes to express
his appreciation and sincere
thanks to Doctor J.H. Reedy
for his assistance in the
experimental work, and also
for his aid in writing this
Table of Contents
III. Purpose of Research.
VI . Summary .
The Catalytic Preparation of Hydroxylamine .
I . Introdu c tion .
The question of procuring a good yield of Hydroxylamine
by a simple and inexpensive method has been the subject of consi-
derable investigation by chemists for many years. A few methods
have been suggested and used for its preparation, but in all the
yields are not good, and the methods of separation from by-products
are difficult and not conducive to complete separation. Reduction
of nitrites , nitric acid and nitric oxide to Hydroxylamine by such
reducing agents as sulphurous acid, chromous chloride, hydrogen
sulphide .hydrogen, etc. , have been attempted with but indifferent
success , mainly , because of the fact that a good method of separation
was lacking or that the reduction did not stop at Hydroxylamine,
but continued further to give nitrous oxide, nitrogen or ammonia.
It was noticed by Victor Meyer and others that often some
substance used as a catalyser or by-products of the reactions
would cause the immediate decomposotion of any Hydroxylamine which
might be formed. The urgent need of a catalyser which could be used
to facilitate the reduction of nitric oxide to Hydroxylamine alone
and still not cause the decomposition of the Hydroxylamine formed,
seeias a paramount necessity if we expect to obtain Hydroxylamine
in nearly theoretical amounts.
In 1834 Faraday ' published an article wherein he described
some experiments on the use of platinum sponge as a catalyser.
Among the reactions he experminted with was the reduction of nitric
oxide by means of hydrogen using the platinum sponge as a catalyses
He passed a mixture of hydrogen and nitric oxide slowly over pla-
tinum sponge at room temperature. Reduction of the nitric oxide
took place but his final product was not Hydroxylamine as he ex-
pected but ammonia and water. F.Kuhlmann and Jouve“also working
on the reduction of nitric oxide by hydrogen with the use of pla-
tinum sponge as a catalyser obtained ammonia and water as the
final product, altho Jouve working at temperatures not exceeding
115°C, claims to have obtained 1-2 % of Hydroxylamine.
Cooke working with a mixture of nitric oxide and hydrogen
and using platinum sponge as a catalyser , states that he obtained
ammonia, Hydroxylamine and nitrous oxide, the amounts of which he
does not mention in his paper. He states that if one uses nitric
oxide and hydrogen in the volume ratio of 1-2, the following re-
action will take place
2N0 +- H2 H20 + N20
and for 2 volumes of nitric oxide and 8 volumes of hydrogen the
2N0 + 4H2 —NH20H NH40H
Sabatier and Senderens, - Neogie and Adhicary used nickel and
copper as catalysers. They passed a mixture of nitric oxide and
hydrogen thru a glass tube which contained finely divided nickel
or copper at temperatures ranging from 150-250 'C. The resulting
product was ammonia and nitrogen.
According to Divers and Hagaf Dummreicher* and Chesneau,^
Hydroxylamine and ammonia are produced when nitric oxide is passed
thru a series of gas-washing bottles containing tin and cone,
hydrochloric acid.. The yields, however, are small and the separa-
tion of the Hydroxylamine hydrochloride is not easily accomplished.
Chesneau 1 ' experimenting with a solution of chromous chloride
claims to have reduced nitric oxide to Hydroxylamine and ammonia.
He points out that a rapid constant amount of nitric oxide must
be passed into an acid solution to form Hydroxylamine, otherwise
a slow stream will cause the formation of ammonia.
Ludwig and Hein, Divers and Haga" published papers in which
they state that Hydroxylamine can be obtained in considerable
amounts if nitric oxide is passed slowly into a heated mixture
of tin and hydrochloric acid. They do not state the yields ob-
tained by this method.
Chromous chloride solution according to Chesneau and Kohl-
schutter" reduces nitric oxide to ammonia in neutral solutions
while in acid solution it reduced to Hydroxylamine . The same
authors also found that hydroiodic acid reduces nitric oxide to
ammonia and nitrous oxide.
Dummreicher reports that stannous chloride in strongly acid
solution will reduce nitric oxide to Hydroxylamine in small
amounts and not readily.
Hans Ziehl attempted to prepare Hydroxylamine by the reduc-
tion of nitric oxide using a colloidal solution of platinum, which
he prepared by reducing a sightly alkaline solution of chlor-
platinic acid with hydrazine and adding a small amount of gum
arabic. Equal volumes of hydrogen and nitric oxide were passed
under pressure into a pressure bottle containing the colloidal
platinum. The bottle is connected to a shaking devise and sha-
ken vigerously. Ziehl found that no Hydroxylamine was formed by
this method but that his final product consisted of ammonia and
nitrogen. A mixture consisting of 2 volumes of nitric oxide and
3 volumes of hydrogen was tried but as before he obtained ammonia
and nitrogen. They found that 82.34$ of the nitric oxide was
changed to nitrogen while 15.73$ became ammonia.
Divers and Haga'have succeeded in obtaining Hydroxylamine
in the following manner. If sodium sulphide and sodium nitrite
in solution are mixed, then acidified and boiled, Hydroxylamine is
formed, and when the sulphide is in the proportion of 2 mols to
1 mol of the nitrite, and the hydrochloric acid added very slowly,
almost all of the nitrogen is found on titration with iodine to
have been converted into Hydroxylamine.
NaN02 -r 2Na2S03 + HOH t RHCL — ^NH20H,HC1 3Nacl 2NaHS04
On evaporating the acid solution, separating the sodium salts by
absolute alcohol and evaporating again, Hydroxylamine sulphate
separates out. Further experiment proved that sodium meta-
sulphide used with sodium nitrite gave the best yield of Hydroxy-
In 1387 Raschig reported that Hydroxylamine can be gotten
from a nitrite by sulphonation followed by hydrolysis. Divers
.... it m 'M 111. I
and Haga working on the suggestion given by Raschig's work used a
concentrated solution of 2 raols of commercial sodium nitrite, 1 mol
of sodium carbonate and then treated the solution with sulphur
dioxide until just acid, while it was kept well agitated at2-3'"C
below zero. It was claimed by them that at this temperature sul-
phur dioxide will not act on Hydroxylamine but will reduce the
nitrite completely. At this temperature the conversion of the ni-
S * 2
trite into oximido-sulphonate^'^v, c r<? A< * appears to be complete.
~ O A'<X’
When gently warmed with a few drops of sulphuric acid, the oximido-
sulphonate rapidly by hydrolysis, with mark rise in temperature into
oxyamido-sulphonate and sodium acid sulphate. The solution of the
salts is kept at 90-95 G for two days, by the end of which time all
the oxyamido-sulphonate will have hydrolysed into Hydroxylamine
B. B.Adhikary in writing on the reduction of nitric oxide
by contact action of metals and metallic oxides states that he
passed a mixture of nitric oxide and hydrogen over gold, silver,
magnesium, tin, antimony , bismuth and iron at various temperatures and
in all cases ammonia and water were the final products.
E.P.Schoch and R.H. Pritchett after trying various other
methods found that the preparation of Hydroxylamine by the electro-
lytic reduction of nitric acid according to the method of Julius
Tafel, to produce the largest yields. The apparatus used was iden-
tical with that of Tafel f s except that the anode is a lead rod or
pipe about one inch in diameter; this was used in place of the
graphite anode employed by Tafel, because they found it necessary to
use dilute sulphuric acid in the anode compartment. The Hydroxyla-
mine hydrochloride was freed from the accompanying ammonium chloride
produced, by extraction with cold absolute alcohol. They claim to
have obtained about 80 % of the theoretical amount possible.
Other work too numerous to mention has been done upon the
preparation of Hydroxylamine , but the methods are only of theoretical
importance and therefore will not be mentioned here.
III. Purpose of Wo rk.
As it will be seen from the preceding pages, very few exper-
iments have been performed using a catalyist for promoting the re-
duction of the nitric oxide to Hydroxylamine. In view of the diffi-
cult methods used for recovering Hydroxylamine from the by-products
by the reaction it was deemed that, if possible , some method might be
devised for preparing Hydroxylamine by the use of two gases, one of
them to be nitric oxide and the other some reducing gas as sulphur
dioxide, hydrogen, hydrogen sulphide, etc . , in the presence of a cat-
alyist. In this manner interfering by-products would be eliminated
and the Hydroxylamine easily and quickly separated. It will be noti-
ced from Ziehls and Sabatier and Senderens (loc. cit.) work using
colloidal platinum and nickel respectivily , that the reduction does
not stop at Hydroxylamine but continues to ammonia. To secure a
catalyist which would promote the reduction of nitric oxide to
Hydroxylamine and stop there, seemed to be the key to the solution of
this problem, so it was thus made the object of this paper. It was
^ | ijg§
thot advisable to undertake various methods of reduction and deter-
mine the effect different catalyist had on the reaction. Once the
reduction of nitric oxide to Hydroxylamine was accomplished, a
method 02 separation and purification would be a comparatively sim-
ple task because of the absence of interfering substances.
Altho Schoch and Pritchett (loc.cit.) xhave obtained
Hydroxylamine by the electrolytic reduction of nitric acid and
claim to have obtained as much as 80 % of the theoretical yield, we
did not attempt to obtain Hydroxylamine by an electrical method but
have confined ourselves to its production by strictly chemical
The method to be used for the detection Hydroxylamine was
the reduction of Fehling's solution. Very minute amounts of
Hydroxylamine of its salts are sufficient to cause the formation
of the brown copper oxide.
IV. Experimental .
According to Sabatier and Sendereiis (loc.cit.) the activity
of nickel as a catalyist is nil at low temperatures, but at 250-300' 0
nickel is quite active. It was decided to see if nickel at a tem-
perature of 100-115°C would catalyse the reduction of nitric oxide
to Hydroxylamine, and not to ammonia. The apparatus used is shown
on Figure 1 .
Preparation of Catalys err-The catalyser was made by melting
nickel nitrate in its own water of crystalization in a nickel cruci-
ole and then inpregnat ing animal charcoal with the solution. The
inpregnated charcoal was then heated in the crucible to form the
nickel oxide. It was placed in a glass conbustion tube heated to
^50-300 C,and reduced with a stream of hydrogen for three hours.
Procedure — 3he tube, after the reduction of the nickel
oxide had taken place, was allowed to cool slowly to 105 G with
hydrogen still passing thru. A mixture of 2 volumes of hydrogen
and one volume of nitric oxide was slowly passed thru the tube, the
temperature being maintained about 110 C,the alkaline gases pro-
duced were absorbed in dilute hydrochloric acid. When the run was
completed this acid solution was examined for Hydroxylamine by
adding a little of the solution to Fehling's solutions. No reduc-
tion of the Fehling's solution occured which proved the absence of
Hydroxylamine. On opening the tube it was found to smell very
strongly of ammonia. The hydrochloric acid solution was evaporated
lo dryness on a water bath, the residue broken up and again tested
for Hydroxylamine and ammonia. No Hydroxylamine hydrochloride was
found to be present but on heating a little of the residue with so-
dium hydroxide , the odor of ammonia was easily detected. Another
run was made using equal volumes of nitric oxide and hydrogen but
as before ammonia was the final product.
A statement is found in many text books that Hydroxylamine
can be prepared by passing nitric oxide thru a solution of tin-
dissolving in hydrochloric acid. No mention,however , is made in
regards to the amounts obtained and so in order to get some idea
of the yield of Hydroxylamine produced, by this method, it was deci-
ded to repeat the procedure using metallic mercury as a catalyser.
Procedure - -The apparatus is shown in Figure 2. In each of
the gas washing bottles was placed tinfoil cut into very small
squares, and covered with a dilute solution of hydrochloric acid.
The two gases nitric oxide and hydrogen in equal volumes were
bubbled thru the bottles at a uniform rate of approximately 30
bubbles per minute. The tin in dissolving gives up nascent hydro-
gen according to the equation
Sn 2H01 = SnC12 + H2
which was expected to x-educe the nitric oxide while stannous chlor-
ide ana mercury might catalyse the reduction. After fourteen liters
of each gas had been passed thru the bottles, the solutions from
each of the bottles were combined in a large Erlenmeyer flask, water
added and the tin precipitated out with hydrogen sulphide. Two pre-
cipitations were necessary to separate alx of uhe tin. T**e solution
was then filtered, washed and the filtrate evaporated to dryness on
a water bath, ihe residue was examined for Hydroxylamine but no
reduction of Fehling’s solution occured. It was then tested for
ammonia which was found to be present, mercury being omitted anot-
her run similar to the first gave ammonia as the only product.
It was apparent from the preceding experiments that if
satisfactory yields are to be obtained a more intimate and longer
contact should be made between the gases and the catalyser* With
this idea in mind an apparatus as shown in Figure 3, was constructed.
Apparatus - -This consisted of an tight cast iron cylinder
about .3 feet tall and 8 M in diameter. The valve at the top was used
to regulate the flow of the gases while the one at the bottom was
connected with the water main by means of which, water could be for-
ced in compressing the gases to o.ny required pressure up to 40#.
By means of a hollow copper „ube bent in spiral shape the gases
could be connected to a pressure bottlewhich was mounted on a
shaking devise. Nitric oxide was prepared by mixing in a flask,
200 grams of ferrous sulphate with 40 grams of potassium nitrate
and dropping hot dilute sulphuric acid on the mixture, the gas evol-
ved being collected in gasometers. The gas cylinder was filled
with water, the hollow copper tube connected with the gasometer and
the gas forced in under a water head contained in a connecting
gasometer. The valve at the bottom of the cylinder being opened
simultaneously with the valve at the top. After twelve liters of
nitric oxide had been forced in both valves were closed and connec-
tion made with a hydrogen tank. The upper valve was then opened
and hydrogen forced in until the gauge on the cylinder showed 25#
pressure, after which the valve was closed. In the pressure bottle
was placed a colloidal solution of platinum prepared according to
directions given by H.L.Lockte of the University of Illinois.
Prepa r ation of Gatal.yist --About .3 gram of platinum was
dissolved in aqua regia and evaporated to dryness twice, then taken
up with hydrochloric acid. The chlor-platinic acid thus formed
was poured into a beaker containing 250 c.c.of water made slightly
alkaline with sodium hydroxide.
Approximately .3 gram of gum arable in water solution was added,
and a few crystals of hydrazine hydrochloride were dropped into the
solution. Reduction took place almost immediately after which the
solution was made acidic with hydrochloric acid. The solution was
poured into the pressure bottle, the bottle evacuated and connection
made to the gas cylinder.
Procedure - -The motor was started and the solution
shaken for six hours during which time the reading on the gauge
was carefully noted. No decrease on the gauge reading was observed
during the run. The bottle was then disconnected and the solution
poured into a flask containing a volume of acetone equal to that
of the solution. This acetone solution wa3 allowed to stand over
night and then filtered to remove the precipitated platinum. The
filtrate was then tested for Hydroxylamine with Fehling '3 solution,
but no reduction was observed. On evaporating the solution to dry-
ness no residue was left proving that nitric oxide and hydrogen in
the presence of colloidal platinum would not react.
Platinum as the Catalyist --A active form of platinum has
been developed in the organic division of the University of Illinois,
which has been very successful in reducing many organic compounds.
It was thot that it might also promote the reduction of nitric oxide.
Preparation of the data! yiist - -About .4-. 5 gram of platinic
chloride was dissolved in a mixture of 5 grams of sodium nitrate
I 1 $
and 4 grams of potassium nitrate and the mixture evapotated to dry-
ness on a water bath. It was then fused to a quiet liquid and
allowed to cool, after which it was dissolved in water and filtered.
The platinum precipitate on the filter paper was washed with water
until free from salts. It was then washed into the pressure bottle
and the filter paper saved to be used again to filter off the plat-
inum after the run was completed.
Procedure - -The solution in the pressure bottle was made
acid with hydrochloric acid, the bottle evacuated and connections
made. The bottle was shaken for six hours, the solution removed,
filtered and evaporated to dryness. No residue was left showing
that the platinum used as a catalyser did not have any effect in
aiding hydrogen reduce nitric oxide.
Mercury as the Catalvist - -Using the same pressure appar-
atus as previously described, 15 grams of mercurous chloride and
20 grams of stannous chloride were placed in the pressure bottle
and 200 c.c. of water containing 15c. c. of dilute hydrochloric
acid were added. The bottle was evacuated and connections made
with the gas cylinder. The bottle was shaken for six hours and the
gauge reading carefully observed. The mercurous chloride was re-
duced to black metallic mercury by the stannous chloride. It was
thot that the stannous chloride in conjunction with the hydrogen
formed by the reaction would act as a reducing agent in the pre-
«ence of metallic mercury as the catalyist. The gauge reading
showed no decrease after the six hours. The solution was removed
from the flask, almost neutralized by sodium hydroxide and the tin
precipitated out by hydrogen sulphide. A small amount of the mer-
cury was also precipitated by the hydrogen sulphide but the major
amount was removed when the solution was filtered. The solution
was then evaporated to dryness on a water bath and the residue tested
for Hydroxylamine. The residue was composed completely of sodium
chloride, no Hydroxylamine or ammonia being formed.
Reduction by Chromous Chloride --Chesneau and Kohls chutter
(loc.cit.)in their paper on the reduction of nitric oxide by means
of chromous chloride found that when nitric oxide was passed into
a neutral solution of chromous chloride that ammonia would be the
final product while in an acid solution Hydroxylamine would be
formed. They state, however, that nitric oxide must be passed into
the acid solution of chromous chloride in order to secure Hydroxyl-
amine, otherwise ammonia would be formed. A run was therefore made
using chromous chloride in ian acid solution as a reducing agent.
Preparation of the Chromous Chloride - -Metallic chronium
was ground up to a fine powder and 100 c.c. of water and 50 c.c. of
hydrochloric acid added. The mixture was then poured quickly into
the pressure bottle which was then evacuated and connections made
with the gas tank.
Procedure - -The bottle was shaken for ten hours after which
time the solution was removed, filtered and made alkaline with sodium
hydroxide which precipitated all of the chronium. This was filtered
off and the solution tested for Hydroxylamine. No reduction of the
Fehling's solution took place. ihe solution was evaporated slightly,
then made acidic, evaporated to dryness, and again tested for Hydro x-
ylamine. After a negative result had been obtained it was tested
for ammonia which was found to be present in considerable amounts.
It is evident that the chroinous chloride caused the reduction to
procede to ammonia and not to Hydroxylamine. It was thot, however,
in view of Chesneau and Kohl s chut ter ' s work that some Hydroxylamine
should have been formed. In order to ascertain if the above authors
really secured Hydroxylamine as they claim, their work was repeated.
The apparatus used is shown in Figure 4. Nitric oxide from a gas-
ometer was passed rapidly into an acid solution of chromous chloride
protected from air by a layer of petroleum ether. The residual gas
was collected in another gasometer and again passed thru the chrora-
ous chloride solution. This procedure was repeated several times,
until a marked decrease in the volume of nitric oxide was observed.
The solution was poured into a separatory funnel and the chroinous
chloride solution drawn off. It was then made alkaline with sodium
hydroxide and the precipitated chromium filtered off. The filtrate
was evaporated to dryness and the residue tested for Hydroxylamine.
No reduction of the Fehling's solution took place. It was then
examined for ammonia \vhich was again found to be present in consider-
The experiment was again repeated, all possible care in
following directions was taken, samples of the chromous chloride
solution being tested every few minutes, but at no time could any
positive test for Hydroxylamine be obtained. Altho Chesneau and
Kohlschutter claim to have obtained Hydroxylamine in this manner.
we do not believe it possible that Hydroxylamine could be formed
and stay in the solution as Hydroxylamine in the presence of such
a powerful reducing agent as chromous chloride. It may be possible
that Hydroxylamine is formed as an intermediate product, but our
belief is that it is immediately reduced to ammonia.
Nickel as the Catalyser - -In view of previous research and
our own results, it was decided that the platinum group could not be
used as catalysers due to the fact that Hydroxylamine will decompose
in the presence of colloidal platinum and platinum black. In a paper
published by A. Findlay and W. Thomas the products of the decomposi-
tion are said to be ammonia nitrogen and nitrous oxide. B.Adhikary
(loc.cit.) did all his work at temperatures over 100 G. A search of
the literature failed to reveal any statements regarding the use of
lower temperatures. If at over 100° C nickel changes nitric oxide
to ammonia, would it not be possible at temperatures up to 90 G that
the reducing action would not be so strong and instead of reducing
the nitric oxide to ammonia it might stop at Hydroxylamine?
Preparation and Use of the Gatalyist --A nickel catalyser
which had been prepared Dy reducing nickel nitrate, was put into the
pressure bottle, water added, the bottle evacuated and connected to
the gas cylinder. After opening up the cylinder valve, the bottle
was shaken for three hours at ordinary temperature. No decrease
could be observed in the gauge reading. The temperature of the
solution was raised gradually by placing a small flame under the
bottle and surrounding the shaking bottle by an asbestos box to
keep the heat in. A temperature of about 80-90 C could be obtained
in this manner.
The bottle was shaken for three more hours, the flame remo-
ved and the bottle with solution allowed to c^ol while shaking.
The solution was filtered to remove the nickel, and a small amount
of hydrochloric acid added to the filtrate. The latter was evapor-
ated to dryness but no residue was left showing that at tempera-
tures below 100 G nickel did not catalyse the reduction of nitric
oxide in a water solution.
Reduction by Means of ned Phosphorus - -Among the chemical
properties of red phosphorus is listed the fact that concentrated
nitric acid is reduced with almost explosive violence while dilute
nitric acid evolves nitrous fumes in the presence of red phosphor-
us. Because of the reducing action it appeared possible that the
red phosphorus might also reduce nitric oxide. A mixture of the
red phosphorus and water was put into the reactian bottle and nit-
ric acid bubbled thru the solution. In conjunction with this
method, red phosphorus and water were also put in the pressure bott-
le, connection made with the gas cylinder and the bottle shaken for
three hours. The nitric oxide in the gasometer was passed back and
forth several times thru the reaction bottle. The solutions were
taken from the reaction and pressure bottles, filtered and evapora-
ted to dryness after 10 c.c. of hydrochloric acid had been added.
No residue is left proving red phosphorus would not cause the re-
duction of nitric oxide. In another run potassium iodide was add-
ed as a catalyser,but the result was similar to the first as no
Hydroxylaraine was obtained.
The Use o f Sodium Amalgam as the Re ducing Agent - -The reduc-
tion of many organic compounds by sodium amalgam led to the belief
that it might aid in the reduction of nitric oxide. An amalgam
containing .214$ sodium was put into the pressure bottle, connec-
tions made and the bottle shaken for eight hours. It was removed
from the bottle, filtered to remove the amalgam, a small amount of'
hydrochloric acid added and the solution evaporated to dryness.
No residue was obtained.
Catalytic Reduction by Means of Palladium Asbestos
Sabatier and Senderens have shown that in the presence of palla-
dium sponge previously saturated with hydrogen, nitric oxide is com-
pletely converted into water and ammonia. Their work was repeated
by us with the exception that instead of palladium sponge being
used we worked with palladium asbestos. The two gases, nitric oxide
and hydrogen were preheated before passing over the catalyist.
A diagram of the apparatus is shown in Figure 5. Nitric oxide and
hydrogen were passed thru gas-washing bottles containing sulphuric
acid and then thru a short piece of heavy glass tubing about three-
fourths of an inoh in diameter, where they were heated slightly. The
preheated gases were then passed thru the catalyser tube containing
the palladium into a dilute solution of hydrochloric acid. On exam-
ination of the hydrochloric acid solution it was found to contain
ammonium chloride only, no Hydroxylaraine being formed.
Reduction b y Use of Sulphur Dioxide -- In Divers and Haga
(loc.cit.) publication, state that they have obtained Hydroxy lamine
using sodium nitrite and sodium sulphite according to the equation.
NaN02 + 2Na2S03 + HOH +■ 4HC1 = NH20H HG1 3NaCl -f 2NaHS04
It would seem from the above equation that sulphur dioxide is the
active reducing agent. Tanatar, however , claims that sulphur dioxide
will attack Hydroxylamine reducing it to ammonium sulphate. Divers
and Haga's method was repeated by us, all directions being carefully
followed. Sodium nitrite and sodium sulphite were mixed in the pro-
portions as given by the equation, water added and the hydrochloric
acid added very slowly. The solution was evaporated to dryness, an
absolute alcbhol extraction made but no Hydro xyiamine was found to
be present. The method was again repeated but as before no test for
Hydroxylamine could be obtained. It was noticed that on each addi-
tion of the hydrochloric acid a sharp rise in temperature followed.
To determine if this rise in temperature was the cause of the non-
formation of Hydroxylamine, the flask was placed in an ice-salt bath
about -10 J C. The hydrochloric acid was added very slowly to the
solutions of the salts and at no time was the temperature above -5 G
The solution was then placed in evaporating dishes and evap-
orated to dryness. B efore evaporation the solution was boiled for
an hour to expell as much as possible of the sulphur dioxide. On
testing the residue, Hydroxylamine was found to be present, It was
extracted with absolute alcohol and the alcohol distilled oil, leaving
a small amount of Hydroxylamine sulphate as a residue. The separa-
tion of Hydroxylamine sulphate from the by-products, sodium chloride
and sodium acid sulphate is not complete because of the tendency
of these salts to occlude small amounts of Hydroxylamine sulphate.
Several extractions are necessary to completely remove all the
Hydroxylamine sulphate. It is important to note that unless the
reaction is carried out at low temperatures and the hydrochloric
acid added very slowly, no Hydroxylamine sulphate will be formed.
A possible explanation for this fact is that at room temperatures,
sulphur dioxide will attack the Hydroxylamine formed and convert it
into ammonium sulphate, while at temperatures below G^C, sulphur
dioxide will complete the reduction but will not act on the Hydrox-
y 1 am in e formed.
Since Hydroxylamine can be formed by the reduction of a
nitrite, would it not be possible that nitric oxide could be reduced
in a similar manner? Qn account of the very slight solubility of
nitric oxide in water , advantage was taken of the fact that nitric
oxide will form an addition compound with ferrous sulphate in
Water solution. An apparatus such as shown in Figure 6, served the
purpose very well. About 8-10 grams of ferrous sulphate was dis-
solved in 600 c.c. of water and the solution ' poured into a large
wide-mouthed bottle. Nitric oxide made from ferrous sulphate,
potassium nitrate and dilute sulphuric acid was passed into the
water solution until it became a dark brown color. Sulphur dio-
xide made by dropping sulphuric acid on sodium bisulphate was also
passed into the water solution. The bottle was then immersed in
an ice-salt bath and the solution stirred vigorously with a glass
Approximately 10 liters of nitric oxide and 15 liters of
sulphur dioxide were passed into the solution. After shaking for
an hour the solution turned to a white color. It was then removed,
allowed to come to room temperature. A small amount of the sol-
ution was tested with barium chloride, which gave a white precipi-
tate showing that the sulphur dioxide had been oxidized to sulphu-
ric acid» Sodium hydroxide was added to precipitate all the iron
and the solution filtered. The filtrate was made acidic with
sulphuric acid and evaporated to dryness. No test for Hydroxyl-
amine was obtained.
In all probability Hydroxy lamine was immediately reduced by
the ferrous sulphate or by the sulphur dioxide. According to
Tanar (loc.cit.) when a solution of Hydroxylamine sulphate is
saturated with sulphur dioxide, kept over night and evaporated to
dryness on a water bath, ammonium sulphate is formed.
Reaction with Hydraztne --To ascertain whether hydrazine
would reduce nitric oxide, about 10 grams of it in water solution
was put into a bottle and nitric bubbled thru. Examination of
the solution proved that no reduction had taken place.
V. Discussion .
It will be seen from our results that the preparation of
Hydroxylamine by a strictly chemical method is difficult and, in
many cases, without success, the direct cause of the failure to pro-
duce Hydroxylamine by some of the methods tried was due mainly to
the great susceptibility of Hydroxylamine to the action of many
substances which either decompose it as quickly as it is formed or
reduces it at once to ammonia.
It should be noted that low temperatures are conducive to
the production of . Hydroxylamine, higher temperatures causing the
formation of ammonia, nitrogen and nitrous oxide. This fact pro-
hibits the use of such catalyists as nickel, copper , iron, etc . ,
which require temperatures over 100 G before they become active
and thus our work was confined to the use of the platinum group.
It was shown that nickel in a x&ter* solution at 8 Q-9G G does not
cause the reduction of nitric oxide. The action of the catalyist
used in this research either caused the decomposition or reduction
of the Hydroxylamine formed or else had no effect on the reaction.
No catalyser has been found which would promote the reduction to
Hydroxylamine and not to ammonia.
Hydroxylamine sulphate was obtained us using Diver's and
Haga's (loc.cit.) method, but the amount obtained was small and a
complete extraction difficult. The attempt to reduce nitric oxide
by sulphur dioxide in the presence of ferrous sulphate as might
have been expected because of the action of both ferrous sulphate
and sulphur dioxide in decomposing any Hydroxylamine formed.
If it were possible to procure some substance, the addition of which,
would cause the Hydroxylamine to be precipitated as soon as it were
formed, the solution of this problem might be solved.
VI. Summary .
I. Nitric oxide will not be reduced in the presence of
colloidal or finely divided platinum used as a catalyist.
II. At temperatures below 100-C nickel is not active
while at higher temperatures it will promote the reduction of
nitric oxide to ammonia.
III. Strong reducing agents such as chromous chloride
reduce nitric oxide to ammonia, no Hydroxylamine being formed.
IV. Salts of Hydroxylamine in a saturated solution of
sulphur dioxide and in the presence of ferrous sulphate are reduced
to ammonia, if allowed to stand at room temperature for several
V. Substances such as metallic mercury, red phosphorus,
sodium amalgam, stannous chloride, and hydrazine do not cause the
reduction of nitric oxide to proceed to the formation of Hydroxyl-
VII. Bibliography .
1. Faraday: Pogg. Ann. 33-149 (1834).
2. F.Kuhlmann: A. 29,286, (1839).
3. Jouve: Comp. rend. 128,435, (1899).
4. Cooke: C.1327, (1888).
5. Sabatier and Senderen3: Comp. rend. 135,278, (1902).
3. Neogie and Adhicary: C. 463, (l$ll).
Divers and Haga: J.Chem.Soc. 47,623, (1899).
8. Dummreicher : W.Ak.B. 82,560, (1880).
9. Chesneau: C.R. 129,100, (1899).
10. Ludwig and Hein: B.2,671, (i860),
11. Divers and Haga: J.Chem.Soc. 47,623. (1885).
12. Chesneau and Kohlschutter : B. 37,3093,(1904).
13. Dummreicher: Abstract J.Chem.Soc. 331, (1882).
14. H.Ziehl: Doctor’s Thesis "Katalytische Hydrierung von Stick-
stof fverbindungen, G-ottingen. (1914).
15. Divers and Haga: J.CHEM.SOC. vol.LI. 660,(1837). Trans.
16. Divers and Haga: J.CHEM.SOC. vol.59,1665, (1896) Trans .II.
17. Raschig: Chem.Zeit. 12,219. (1887).
18. Divers and Haga: J.CHEM.SOC. Trans. 1565, (1896).
20. B.B.Adhikary : Chem.News, 112, 133-4 (1915).
21. Schoch and Pritchett : J .Am. Chem. Soc . 2042-4, (1916).
22. J.Tafel*. Z. Anorg. Chem. 31, ( 1902). 289, ( 1902).